催化裂化装置加工高氮原料的技术措施

国内某些催化裂化装置原料中的氮含量偏高,由此影响了催化剂的活性、原料的转化率及产品的安定性。分析讨论了这类装置的操作情况及原料中不同氮化物对催化裂化反应的影响因素,提出了加工高氮原料的具体技术措施。     

催化裂化硫平衡及加工高硫原料的影响

介绍了扬子石化2.0Mt/a催化裂化装置硫平衡情况,分析了硫含量对产品收率、产品质量、设备腐蚀的影响。     

催化裂化抗氮中毒技术的研究进展

从调节催化剂酸性或向反应体系外加抗氮剂的角度,介绍了加强催化裂化抗氮中毒能力,以增产汽油、柴油、丙烯或抑焦为目的的研究进展。针对于调变催化剂本身的酸性存在灵活性差、成本高的缺点,认为开发性优价廉的抗氮助剂改善原料质量,减缓催化剂中毒是有前景的抗氮中毒技术。     

催化裂化催化剂碱氮中毒数学模型的研究

利用几种催化剂的催化裂化反应试验数据,通过碱氮中毒模型方程推导和模型参数的估计,建立了评价裂化催化剂抗碱氮中毒活性稳定性的数学模型。关联研究结果表明,降低催化剂分子筛含量和稀土金属含量,以及提高硅铝比和钠含量,有利于提高催化剂抗碱氮中知性稳定性;提高催化剂分子筛含量、硅铝重量比、稀土金属含量,以及降低钠的含量,可提高催化裂化反应速率。     

氮中毒对柴油催化裂化的影响

本文对工业催化裂化催化剂的碱性氮受破坏程度作出了测定。     

催化裂化催化剂碱氮中毒数学模型的研究

利用几种催化剂的催化裂化反应试验数据,通过碱氮中毒模型方程推导和模型参数的估计,建立了评价裂化催化剂抗碱氮中毒活性稳定性的数学模型。关联研究结果表明,降低催化剂分子筛含量和稀土金属含量,以及提高硅铝比和钠含量,有利于提高催化剂抗碱氮中毒活性稳定性;提高催化剂分子筛含量、硅铝重量比、稀土金属含量,以及降低钠含量,可提高催化裂化反应速率。     

催化裂化原料加氢预处理催化剂的研制

为满足FCC原料预处理的要求,开发了一种高脱硫、脱氮活性的FCC原料预加氢处理催化剂。该催化剂以氟改性氧化铝为载体,Ni Mo为活性组分,比表面积为169 m2·g-1,孔容为0.31 m L·g-1,平均孔径为6.5 nm,最可几孔径为3.35 nm和8.00 nm,孔径(4~10)nm占71%,具有大孔容、高比表面积和活性金属组分分散性好等特点。在100 m L固定床加氢试验装置上,以中国石化青岛炼化公司的高硫低氮混合蜡油和江苏新海石化有限公司的高硫高氮焦化蜡油为原料进行加氢活性评价。结果表明,在反应温度370℃、反应压力10.0 MPa、空速1.0 h-1和氢油体积比700∶1条件下,高硫低氮混合蜡油的脱硫、脱氮率分别为98.0%和96.5%,对高硫高氮焦化蜡油的脱硫、脱氮率分别为93.2%和90.0%。催化剂表现出原料适应性强,能有效脱除原料中的硫氮化合物,具有较高的加氢活性。     

催化裂化原料加氢预处理

选择适宜的催化剂和工艺条件,采用催化裂化原料加氢预处理技术可拓宽催化裂化原料的范围,生产优质的催化裂化原料,改善催化裂化产品分布,提高催化裂化汽、柴油产品质量。     

流化催化裂化原料加氢预处理技术综述

综述了流化催化裂化（FCC）原料加氢处理的目的、反应机理、催化剂和工艺流程选择以及操作模式。     

481-3重整预加氢催化剂在高氮原料中的应用

为了降低精制石脑油中氮含量,在重整装置上应用了481-3加氢催化剂,257天的运转情况表明：481-3催化剂具有良好的加氢脱氮、脱硫,脱氯活性,原料适应性强,防冲击能力强,完全能够满足3861重整催化剂对杂重的要求。与法国催化剂HR-306相比,481-3催化剂的反应条件较为缓和,装置开工至今没有发生铵盐堵塞情况,达到了预期的目的。     

吸热燃料催化裂解研究进展

高超声速飞行是航空航天领域的最新前沿技术,是国家科技发展水平的重要标志。吸热燃料是实现高马赫（>5）超声速飞行器实际应用的核心技术之一,因而具有特殊的意义。本文介绍了吸热燃料的研究历程,重点从吸热燃料及其热沉、吸热燃料催化剂、催化剂的结焦以及催化裂解机理等方面对吸热燃料催化裂解进行介绍和评述。分子筛催化剂是吸热燃料催化裂解最具应用前景的一类催化剂,但同时也面临了吸热燃料原料的选择、分子筛骨架结构的改进和表面性质调变、催化剂结焦等基础研究以及催化剂负载、催化剂真实工况模拟等一系列工程应用研究双重挑战。吸热燃料催化裂解机理和动力学研究目前还很薄弱,未能真正深入到分子尺度把催化剂的微观作用与物质形态的变化有机结合,针对这方面的研究还应该大力加强,以更好地为催化剂的设计提供指导意义。     

钒对裂化催化剂的影响及流化催化裂化抗钒助剂的开发

研究了钒对分子筛和催化剂性能的影响 ,并开发出一种高活性固体的流化催化裂化抗钒助剂。随着钒含量的增加 ,分子筛的结晶度、比表面积、孔体积呈单调下降 ;而催化剂的催化活性大幅降低 ,选择性变差。抗钒助剂与其他类型的催化剂复配后 ,显示出较强的抗钒性能 ,能明显改善裂化产物的汽油、焦炭的选择性。     

Four-lump kinetic model for fluid catalytic cracking process

In the fluid catalytic cracking reactor heavy gas oil is cracked into more valuable lighter hydrocarbon products. The reactor input is a mixture of hydrocarbons which makes the reaction kinetics very complicated due to the involved reactions. In this paper, a four-lump model is proposed to describe the process. This model is different from others mainly in that the deposition rate of coke on catalyst can be predicted from gas oil conversion and isolated from the C₁–C₄ gas yield. This is important since coke supplies heat required for endothermic reactions occurring in the reactor. By this model we can also conclude that the C1–C4 gas yield increases with increasing reactor temperature, while production of gasoline and coke decreases.     

Relative reactivities of alkanes in multi-component catalytic cracking reactions

An experimental technique is discussed for measuring relative reactivities of alkanes in the catalytic cracking of multi-component hydrocarbon mixtures over a heterogeneous, Y-zeolitebased catalyst at 250–350 °C. With the technique, ca. 0.1 l of an alkane mixture is evaporated and contacted with a catalyst, after which the mixture of reaction products and the unreacted feed enters the chromatographic column and is immediately analyzed. The technique is used to measure relative reactivities of 21 alkanes in a single experiment. The principal results of these experiments are similar to the results of single-component cracking: alkane reactivity rapidly increases with the increase of the carbon number, and methyl-branched alkanes are more reactive than linear alkanes. However, the variations in alkane reactivities as a function of their molecular weight and skeleton structure differ very significantly between single- and multicomponent experiments.     

催化裂化催化剂再生过程中的氮化学进展

从流化催化裂化待生催化剂中含氮化合物的主要类型和生成机制、再生过程中含氮化合物的转化途径以及降低再生过程中氮氧化物排放的相应控制措施等几个方面,综述了流化催化裂化催化剂再生过程中的氮化学研究进展。     

催化裂化吸附转化加工焦化蜡油工艺

分析了焦化蜡油（CGO）与直馏蜡油（VGO）的性质,焦化蜡油与直馏蜡油性质相差较大,主要表现在焦化蜡油残炭、碱氮化合物、胶质、沥青质及金属含量较直馏蜡油高,催化裂化（FCC）直接掺炼焦化蜡油,会造成转化率降低,产物分布恶化,运转周期缩短。通过常规催化裂化加工焦化蜡油工艺与FCC通过吸附转化工艺加工焦化蜡油比较,得出催化裂化吸附转化加工焦化蜡油工艺可以明显改善产物分布,提高转化率,降低碱氮化合物对催化剂的毒害作用,提高装置的整体经济效益。     

催化裂化催化剂铁污染研究进展

介绍近年关于FCC催化剂铁中毒现象的研究进展。平衡剂上铁存在新鲜催化剂自身铁、原油原有铁和过程铁3个来源,其中,高酸原油的过程铁含量已不容忽视。催化裂化过程中,原料油中以环烷酸铁为主的铁物种不断沉积在催化剂的表面,与催化剂中的钠、氧化硅形成低熔点共熔物,形成覆盖平衡剂表面的光滑结构,堵塞催化剂的孔道,导致汽油产率下降,严重影响装置稳定运行。根据铁中毒的机理研究,提出加强人员技术交流与培训、提高分析检测频次、应用抗铁污染催化剂、铁中毒解决方案等预防和应急措施,为加工高铁含量原料油催化裂化装置的长期稳定运行提供技术参考。     

Modelling the kinetics of fast catalytic cracking reactions

Instantaneous kinetic constants and gasoline selectivities have been determined for catalytic cracking of n-hexadecane. The pulse technique was used in order to model the sequential build-up of coke which occurs on cracking catalyst within a riser transport-line reactor. The total amount of hydrocarbon injected per unit weight of catalyst was between 0 and 10. The mathematical model used to analyze the data was based on the unsteady state mass balance of the microcatalytic reactor with the assumption of plug flow. Results suggest a fast deactivation process during the run with fresh catalyst, while regenerated catalyst showed a slower deactivation. The catalyst regenerated three times evidenced a low apparent activation energy when temperature was increased from 500°C to 550°C.     

Production of steam cracking feedstocks by mild cracking of plastic wastes

In this work the utility of new possible petrochemical feedstocks obtained by plastic waste cracking has been studied. The cracking process of polyethylene (PE), polyethylene-polypropylene (PEPP) and polyethylene-polystyrene (PEPS) has been carried out in a pilot scale tubular reactor. In this process mild reaction parameters has been applied, with the temperature of 530 °C and the residence time of 15 min. The produced hydrocarbon fractions as light- and middle distillates were tested by using a laboratory steam cracking unit.It was concluded that the products of the mild cracking of plastic wastes could be applied as petrochemical feedstocks. Based on the analytical data it was determined that these liquid products contained in significant concentration (25-50 wt.%) of olefin hydrocarbons. Moreover the cracking of polystyrene containing raw material resulted in liquid products with significant amounts of aromatic hydrocarbons too. The steam cracking experiments proved that the products obtained by PE and PEPP cracking resulted in similar or better ethylene and propylene yields than the reference samples, however the aromatic content of PEPS products reduced the ethylene and propylene yields.     

催化裂化油浆利用的技术进展

概述了催化裂化油浆的组成、性质和净化技术,介绍了催化裂化油浆在石油加工、石油化工领域利用的技术进展。分析了油浆在沥青改性、与煤共处理制取沥青改进剂、溶剂脱沥青、强化蒸馏、减黏裂化和延迟焦化工艺中的应用;评述了油浆的深度分离技术及分离所得组分的利用。